Compositions of matter comprising halogenated organic compounds



Jan 8, 1952 B. H. HARTzoG 2 582 200' COMPOSITIONS OF MATTER COMPRISING HOLOGENATED ORGANIC COMPOUNDS Filed Aug. 16, 1949 f M5701. fou,

Pat/e /nmeavmrao INVENTOR. wmf Maase/wrm l Fig. 3 0mm/wc commu/vo IJ/0K0 #17,?7206 mvo TA/Y1. .SIL/cara BY a n Q frei/v6 y Patented Jan. 8, 1952 COIKPOSITION S OF MATTER COMPRISING HALOGENATED ORGANIC COMPOUNDS Buford H. Hartzog, Texas City, Tex., assignor to Monsanto Company, St. Louis, Mo., a

corporation of Ddaware Application August 16, 1949, Serial No. 110,518

I4 Claims. l

The present invention relates to novel compo sitions of matter comprising halogenated organic compounds and ethyl silicate' as a scavenging or corrosion inhibiting material. More specically, the invention relates to apparatus, particularly electrical apparatus such as capacitors, transformers, circuit breakers, cables and the like containing the above compositions.

Halogenated organic compounds, more particularly halogenated aromatic compounds such as chlorinated biphenyl and. chlorinated naphthalene are highly useful electrical insulating materials because of their high dielectric constants, thermal stability, resistance to oxidation, non-flammability and other valuable properties. However, it has been found that when exposed to elevated temperatures and/or high voltages, they partially decompose liberatingk hydrogen halides which have an exceedingly deleterious action on the paper insulation and metal parts of electrical apparatus.

For example, in transformers, circuit breakers and other electrical devices in which arcing occurs, the development of hydrogen halides as a result of the above decomposition presents a serious problem as they decrease the dielectric strength of the composition containing same and cause considerable damage by attacking paper insulation and corroding metal. parts oithe apparatus in which the composition is used. The undesirable effect of the. above decomposition further manifested when` the above halogenated organic compounds are used as capacitor impregnants. Thus, under high operating temperatures and direct current voltages, capacitors impregnated therewith undergo a characteristic type of deterioration which results in an ever increasing leakage current, a short capacitor life, visible localized.V decomposition of the dielectric and corrosion` of the electrodes, Moreovenin the casel of capacitors operating on. alternating. cur"- rent. the decomposition sometimesy results in. an excessive increase in power factor of the dielectric material.

It is, therefore, the object of. the present invention to provide new compositions of matter containing halogena'tedl organic compounds wherein the above objectionable properties are either completely eliminated or substantially re'- duced.

An additional object is to provide transformers. capacitors, circuit breakers, cables and the like containing halogenated organic compounds in combination with a corrosion inhibitor or scavenger wherebyl the deleteriousv action of hy- 2 drogen halides on the paper insulation and metal parts thereof is eliminated or materially reduced.

Another object' is toA provideH a capacitor impregnant containing halogena'ted organic compounds and a corrosion inhibitor or scavenger, Whereby'the deleterious eiect of hydrogen halides on the electrodes and paper insulation of cae' pacitors' is substantially reduced or completely eliminated with the result that the capacitor has a longer useful life and greater dielectric stability than similar capacitors not containing the corrosion inhibitor.

A further object is to provide the cel'lulosic insulation in transformers containing liquid halogenated organic compounds' withv protection against rapid destruction by hydrogen halides evolved as the result of a minor arc within the transformer, thus permitting' complete repair of the assembly by rapid replacement or removal ol' the particular part that gave rise to the'arc and thereby avoiding destruction ofthe entire' paper insulation of the transformer with a consequent high cost of repair.

A still further object is to provide switches, cables and the like containing halogenated organic compounds and a corrosion inhibitor or scavenger which practically eliminates the rusting and corrosion normally accompanying the use of such devices filled with halogenated organic compounds per se.

Other objects and advantages of the present invention will become apparentto lthose skilled in the art as' the description proceeds.

I have discovered that halogen decomposition products can be rendered substantially innocuous and theabove objectives accomplished if, in accordanceA with the present invention, the halogenated organic materials to be protected are associa'ted' with a` relatively small amount of ethyl silicate. This compound possesses the surprising property of inhibiting the deleterious action of hydrogen halides on metals and organic insulation materials without materially affecting the electricai properties of' the halogenated com- `pound or composition with which it is incorporated.

For a more complete understanding oi' the present invention, reference is made to the accompanying drawings and the experimental data hereinafter presented in the specilic examples,

Figure 1 isa front elevation partly in section of a transformer; Figure 2 illustrates a switch in a. similar manner; Figure 3 represents a rolled capacitor; Figure 4 shows a sectional view oi' a portion of the electrodes and dielectric sheets of Parts by Weight chlorinated biphenyl (60% Cl) 60 Trichlorbenzene Ethyl silicate- 0.1

Other well known liquid halogenated hydro-A carbons or mixtures thereof may be used as the insulating and cooling liquid and various other f halogenated organic compounds may constitute a part of such compositions, such as for example, halogenated compounds of naphthalene, toluene, benzene, nitro-diphenyl, diphenyl oxide, diphenyl ketone, diphenyl methane, diphenyl ethane, terphenyls, quaterphenyls, etc.

The presence of 0.05 to 0.1 part by weight of ethyl silicate in the cooling and insulating liquid will not only substantially reduce the deleterious effect of such liquid on organic insulation but will also greatly reduce the corrosion of the metal parts vof the transformer which come in conta-ct therewith in the presence or absence of air.

The switch shown in Figure 2 comprises a casing 6', xed contacts 1 and 8, and movable con'- tacts 9 and I0 which cooperate therewith. The movable contacts are mounted upon a support I I which in turn is operatively connectedl to actuating levers I2. The following is illustrative of a suitable arc quenching liquid which may be used in this device, it being understood that the invention is not limited thereto.

Parts by weight Chlorinated biphenyl (55% Cl) S() Trichlorbenzene 20 Ethyl silicate 0.05

innocuous with the result that switches provided therewith are substantially free from the corrosion normally accompanying the use of such devices filled with halogenated organic compounds per se.

The capacitor shown in Figure 3 is made up of alternate layers of metal foil such as aluminum or tin foil separated by sheets of dielectric material. `It is produced by interleaving two dielectric sheets, such as linen or kraft paper, with the metal foil, and rolling the interleaved sheets in the conventional manner. The rolled capacitor is then impregnated with the dielectric coni-il position by any suitable process, such asv Vacuum impregnation with chlorinated biphenyl having dissolved therein a small proportion of ethyl silicate. The capacitor is then placed in a protective case or otherwise used as desired.

The following range of compositions is illustrative of suitable capacitor impregnants:H

COMPOSITION I Per cent by weight Liquid chlorinated biphenyl, particularly chlorinated biphenyl containing from 42% to 60% by weight of chlorine 0-100 Conventional chlorinated organic dielectric materials About 10o-0 Ethyl silicate 0.01-1

COMPOSITION II Parts by weight Chlorinated biphenyl (42%-60% Cl) '75 Trichlorbenzene 25 Ethyl silicate 0.1

Oi' the above range of compositions, the preferred capacitor impregnant is one having the following composition:

Parts by weight Chlorinated biphenyl (55% Cl) 75 Trichlorbenzene 25 Ethyl silicate 0.1

The presence of ethyl silicate in chlorinated biphenyl or other halogenated organic cornpounds provides excellent protection against the deleterious action of halogen decomposition products on metal, paper and other organic insulation material and consequently capacitors provided therewith will have a longer useful life and greater dielectric stability than similar capacitors containing halogenated organic compounds per se. Moreover, capacitors containing the above compound will not exhibit an ever increasing power factor With time when operated at high temperatures and voltages as is typical oi' capacitors impregnated with halogenated organic materials which are not associated with one of the above corrosion inhibitors.

Figure 4 shows a section of one turn the finished rolled capacitor illustrating the alternate electrodes and dielectric layers. In accordance with the present invention, the nished capacitor contains a halogenated organic compound, preferably chlorinated biphenyl, and a minor proportion of ethyl silicate.

The cable of Figure 5 comprises a core I3, cable conductors I4, insulation consisting of paper or other suitable material I5 and a casing I6. The space between the insulated conductors and the casing is filled with a mixture of ethyl silicate and any of the liquid chlorinated organic compounds mentioned above. Such a composition may consist of a mixture of the following ingredients, but it is to be clearly understood that the invention is not restricted thereto.

Parts by weight Chlorinated biphenyl (60% Cl) 50 'Irichlorbenzene 50 Ethyl silicate About 0.1

The experimental data hereinafter presented illustrate in a striking manner the scavenging or corrosion inhibiting action of ethyl silicate on dielectric compositions containing halogenated organic compounds. In accordance therewith, the effect of the corrosion inhibitor is brought out by showing and comparing the action of an HCl-saturated halogenated dielectric composition, with and without the inhibitor, on organic dielectric materials such as paper. The effectiveness of the inhibitor is manifested by the protection it affords paper against attack by hydrogen chloride and the'degree of attack is indicated by the extent to which the tensile strength of the Peper is decreased. This will be rendered more Six strips of manila wrapping paper (6 x 1") were humidied at 65% R. H. at 'l0o F. for a period of 48 hours and subjected to tensile strength tests. These tests were run on a Scott IP-2 serigraph with a jaw separation of 3 inches and a rate of travel of 34.5 seconds for a loaol of 40 lbs. The result of these tests, being the average of 6 breaks, was as follows: Tensile strength of paper samples, 46,2-1bs./in.

Example II Six stripsof the same pieceot manila wrapping paper (7 x 1") were allowed to soak at a. teni perature of 75 C. for 11A hours in an HC1 sai'- urated solution consisting' oi 60 parts by weight of chlorinated biphenyl (60% C1) and 40 parts by weight of trichlorbenzene and at the end ol`l this operation, the papers were soaked for minutes in benzene, another 15 minutes in methanol and dried. After cutting one half inch from each end of the dried paper strips, they were subjected to the above tensile strength tests with the following result: Tensile strength of impregnated paper` samples, 11.5 lbs/in.

These examples demonstrate that HC1 had a highly deleterious action on the samples since the tensile strength of the paper changed from 46.2 lbs/in. to 11.5 lbs/in., a. decrease in tensile strength of approximately 75%.

Example III The foregoing example was repeated using samples of the same paper and the same impregnant except that 0.1 partr by weight of ethyl silicate was added. 'I'he tensile strength of the impregnated paper was found'to be 25.0 lbs/in., thus demonstrating that the above compound is a highly effective material for rendering halogen decomposition products such as HCl innocuous to paper or other fibrous organic dielectrics.

The following table illustrates the electrical properties of the dielectric composition consisting of 60 parts by Weight of chlorinated biphenyl (60% C1) and 40 parts by weight of trichlorbenzene and also shows the effect thereon of adding 0.1 part by Weight of ethyl silicate.

halogenatod organic compoundsl generally. Thus. the above compound may be used as a scavenger or corrosion inhibitor for chlorinated naphthaiene, chlorinated diphenyl ketone, chlorinated 5 diphenyl oxide, chlorinated diphenyl methane.

chlorinated diphenyl ethane, chlorinated benzene, chlorinated toluene. chlorinated nitro diphenyl, chlorinated alkylated benzenes, chlorinated a1- kylated biphenyls, ethyl trihclorbenzene, ethyl tetrachlorbenzene, ethyl pentachlorbenzene, chlorinated terphenyls, chlorinated quaterphenyls, chlorinated parafnic hydrocarbons, chlorinated alicyclic hydrocarbons, chlorinated oxygen-containing organic compounds, chlorinated rubber. chlorobutadiene polymers, chlorinated fats, chlorinated vegetable oils, chlorinated animal oils, chlorinated mineral oils or mixtures of two or more of these. In place of the chlorinated compounds, the corresponding iluorine, bromine and iodine derivatives may be used. In fact. any halogenated organic compound or composition which tends by reason of its halogen content to cause corrosion of metals or dehydration of paper or organic fibrous insulation, may be rendered f substantially innocuous by means of ethyl silicate.

The method of incorporating ethyl silicate varies with the halogenated organic compound or composition. If the compound or composition is liquid at room temperature, the above compound is merely dissolved therein in suitable concentrations; if it is a solid, the ethyl silicate is blended therewith by the use of solvents or swelling agents or by means of mixing rolls, etc. In the case of halogenated polymers, the silicon compound may be incorporated before, during or after polymerization of the corresponding monomers.

The quantity of ethyl silicate used varies with the halogenated organic compound or composi- In general, satisfactory results are obtained by employing this compound in an amount varying from 0.05% to 4% and preferably from 0.05% to 0.1% by weight of the halogenated organic compound or composition, but it is to be understood that the invention is not limited thereto as slightly lower and somewhat higher concentrations may be employed. Stated broadly, the above compound may be used in amounts varying from 0.01% by weight up to and above the limit of its solubility in the halogenated organic compound or composition. In most in- Dielectric Dielectric Volume Strength, Constant, Resistivity 0.1in. 1 kc., 100 C. 500 V. D. C., Gap, C. 100 C.

U. Chlorinated biphenyl (60% Cl), 60 parts by wt. 43 3. 8 i00 10\ Trichlorbenzene, parts by wt Ollijlorintated biphenyl Cl), 60 parts y w Trichlorebenzene, 40 parts by wt e. 34 3 9 uoxlo Ethyl silicate, about 0.1 part by wt.

The above experimental data indicate that ethyl silicate does not seriously affect the electrical properties of the halogenated organic compounds associated therewith and that, therefore, such compositions are eminently suitable for use in transformers, capacitors, switches, cables and other electrical devices.

The description of the present invention has been directed primarilyto compositions containing chlorinated biphenyl, trichlorbenzene and ethyl silicate, but it is to be understood that the invention is not restricted thereto but embraces mi stances, it is desirable not to exceed the solubility limits of the ethyl silicate, but there are some applications such as heat exchanging operations in which this may be done witout harmful effects.

As widely different embodiments of this invention may be made without departing from the spirit thereof, it is to be understood that the invention is not limited to the specic embodiments except as dened in the appended claims.

I claim: 1. A composition of matter consisting essen- :attaccov 7 ltially of a halogenated aromatic compound and as a scavenger therefor a suiiicient amount of ethyl silicate to render the decomposition products of said halogenated aromatic compound substantially innocuous.

2. A composition of matter consisting essentially of a chlorinated aromatic compound and as a scavenger therefor ethyl silcate, said silicate being employed in an amount Varying from about 0.01% up to and above the limit of its solubility in said composition. y 3. A heat transfer and dielectric composition consisting essentially of chlorinated biphenyl and as a scavenger therefor about 0.05% to about 4% by Weight of ethyl silicate.

4. An insulating and cooling medium for electric apparatus. consisting essentially of a liquid chlorinated biphenyl and as a scavenger therefor about 0.05% to about 4% by weight of ethyl silicate, said chlorinated biphenyl containing from 42% to 60% by Weight of chlorine.

5. A dielectric composition consisting essentially of chlorinated biphenyl and as a scavenger therefor about 0.05% to about 0.1% by Weight of ethyl silicate, said chlorinated biphenyl containing from 42% to 60% by Weight of chlorine.

6. A dielectric composition consisting essentially of chlorinated biphenyl and as a scavenger therefor about'0.0l% to 1% by Weight of ethyl silicate.

7. A dielectric composition consisting essentially of chlorinated biphenyl and as a scavenger therefor about 0.1% by weight of ethyl silicate.

8. A dielectric composition consisting of about 60% by weight of chlorinated biphenyl, about 40% by weight of trichlorbenzene and about 0.05% to 4% by Weight of ethyl silicate, said chlorinated biphenyl containing about 60% by Weight of chlorine.

9. An insulating and cooling composition for 4 electrical apparatus consisting essentially of a liquid chlorinated biphenyl and as a scavenger therefor about 0.05% to about 0.1% by weight of ethyl silicate.

10. An insulating and cooling composition for electrical apparatus consisting of about 60% by weight of chlorinated biphenyl, about 40% by weight of trichlorbenzene and as a scavenger therefor about 0.1% by Weight of ethyl silicate.

1l. An electric arc quenching composition consisting of about 80% of chlorinated biphenyl, about 20% by Weight of trichlorbenzene and as a scavenger therefor about 0.05% by weight of ethyl silicate.

12. An electric arc quenching composition con sisting of about 50% by Weight of chlorinated biphenyl, about 50% by weight of trichlorbenzene and as a scavenger therefor about 0.1% by weight of ethyl silicate.

13. A capacitor impregnant having substantially the following composition:

Per cent by weight Chlorinated biphenyl containing from 42% to 60% by weight of chlorine 0-100 Chlorinated aromatic compound other than chlorinated biphenyl About 100-0 Ethyl silicate 0.01-4

14. A capacitor impregnant consisting of about 75% by Weight of chlorinated biphenyl (42%- 60% chlorine), about 25% by Weight of trichlorbenzene and as a scavenger' therefor about 0.1% by Weight of ethyl silicate.

BUFORD H. HARTZOG.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 1,931,455 Clark Oct. 17, 1933 2,391,686 McLean Dec. 25, 1945 2,468,544 Clark Apr. 26, 1949 

